CN113447552A - Enzyme-free glucose electrochemical sensor and preparation method thereof - Google Patents
Enzyme-free glucose electrochemical sensor and preparation method thereof Download PDFInfo
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- 239000008103 glucose Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 9
- XXEUGVMTDOMTGW-UHFFFAOYSA-N [Cu]=S.[Co].[Ni] Chemical compound [Cu]=S.[Co].[Ni] XXEUGVMTDOMTGW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 31
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 12
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 230000002255 enzymatic effect Effects 0.000 claims description 3
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 12
- 210000002966 serum Anatomy 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 10
- 230000004044 response Effects 0.000 description 10
- 238000002791 soaking Methods 0.000 description 6
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 5
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 5
- 239000011668 ascorbic acid Substances 0.000 description 5
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 5
- 229960003638 dopamine Drugs 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 229940116269 uric acid Drugs 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 206010012601 diabetes mellitus Diseases 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910002440 Co–Ni Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
Abstract
The invention discloses a preparation method of an enzyme-free glucose electrochemical sensor, which comprises the following steps: (1) pretreating a substrate; (2) preparing a mixed metal ion solution and a sulfide solution; (3) preparing a copper-cobalt-nickel sulfide modification layer on a substrate in an in-situ growth manner; (4) drying the prepared copper-cobalt-nickel sulfide electrode; (5) and (4) taking the copper-cobalt-nickel composite sulfide electrode prepared in the step (4) as a working electrode, forming a three-electrode system with a counter electrode and a reference electrode, and connecting the three-electrode system with an electrochemical workstation to form an electrochemical sensor, thus obtaining the copper-cobalt-nickel composite sulfide enzyme-free glucose electrochemical sensor. The invention uses the copper-cobalt-nickel composite sulfide to construct a novel enzyme-free sensor, is applied to high-sensitivity detection of the glucose content in human serum, and shows wider linear range, extremely low detection limit and good anti-interference capability and stability.
Description
Technical Field
The invention belongs to the field of biochemical sensors, and relates to a copper-cobalt-nickel composite sulfide enzyme-free glucose sensor and a preparation method thereof.
Background
Diabetes has become one of the chronic diseases seriously harming human health, and the glucose content in human body needs to be detected quickly, accurately and continuously in order to prevent and monitor diabetes.
Compared with spectrophotometry or chromatography, the electrochemical detection method has the advantages of high sensitivity, quick response, easy preparation and carrying, and the like. Glucose sensors containing enzymes are widely used in the market at present, but the enzymes are high in cost, are easy to be inactivated by the influence of external environment, and seriously affect the reliability of detection results. Therefore, the preparation of the enzyme-free glucose sensor with low cost, high sensitivity and high stability becomes a research hotspot.
Noble metals (Pt, Au, Ag) and alloys thereof can catalyze glucose efficiently, but the cost is high, and the method is not beneficial to popularization. Transition metals (Cu, Co and Ni) and compounds thereof have good catalytic performance, and transition metal nanoparticles, oxides, sulfides and the like are used in the non-enzymatic glucose sensor. The catalytic activity of single transition metal sulfide is not high, so we developed a copper cobalt nickel complex sulfide enzyme-free glucose sensor.
Disclosure of Invention
The invention aims to provide an enzyme-free glucose sensor with a wider linear range, an extremely low detection limit, and good anti-interference capability and stability.
Another object of the present invention is to provide a method for preparing the enzyme-free glucose sensor.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing an enzyme-free glucose electrochemical sensor comprises the following steps:
(1) pretreating a substrate;
(2) preparing a mixed metal ion solution and a sulfide solution;
(3) preparing a copper-cobalt-nickel sulfide modification layer on a substrate in an in-situ growth manner;
(4) drying the prepared copper-cobalt-nickel sulfide electrode;
(5) and (4) taking the copper-cobalt-nickel composite sulfide electrode prepared in the step (4) as a working electrode, forming a three-electrode system with a counter electrode and a reference electrode, and connecting the three-electrode system with an electrochemical workstation to form an electrochemical sensor, thus obtaining the copper-cobalt-nickel composite sulfide enzyme-free glucose electrochemical sensor.
Preferably, in the step (1), the substrate is copper foam. The pretreatment is to cut the foam copper into 0.8 multiplied by 1.5 cm2Blocks of (4) were sonicated in acetone and ethanol at 100kHz for 10 min each.
Further, the mixed metal ion solution is a cobalt-nickel ion mixed solution, and the mixed metal ion solution is a cobalt-nickel ion mixed aqueous solution, and the sulfide solution is a sodium sulfide aqueous solution.
Preferably, in the step (2), the molar ratio of cobalt to nickel in the cobalt-nickel ion mixed solution is 1: 1, the total concentration of the mixed solution is 0.5M, and the concentration of the sodium sulfide solution is 0.5M.
Preferably, in the step (3), the copper-cobalt-nickel composite sulfide modification layer is prepared by in-situ growth on the substrate by using an ion layer adsorption and reaction method: and immersing the electrode substrate into the cobalt-nickel mixed solution for 1 min, vertically placing the electrode substrate on filter paper for 15 s by using a pair of tweezers, immersing the electrode substrate into a sodium sulfide solution for 1 min, and washing the electrode substrate by using water to obtain the copper-cobalt-nickel composite sulfide electrode.
Preferably, in the step (4), the drying temperature of the copper-cobalt-nickel composite sulfide electrode is 60 ℃, and the drying time is 3 hours.
Preferably, in the step (5), the counter electrode is a platinum wire electrode, and the reference electrode is Ag/AgCl/3M KCl.
The invention has the characteristics and beneficial effects that:
1. the invention uses the copper-cobalt-nickel composite sulfide to construct a novel enzyme-free sensor, is applied to high-sensitivity detection of the glucose content in human serum, and shows wider linear range, extremely low detection limit and good anti-interference capability and stability.
2. The preparation condition is mild, high-temperature reaction and electrodeposition preparation are not needed, the preparation method is simple and rapid, the time is saved, and the test efficiency is improved.
3. The copper-cobalt-nickel composite sulfide is prepared by taking the foamy copper as a substrate and a copper source and adopting an ion layer adsorption and reaction method, has fine particles and a large specific surface area, catalytic sites are added to the porous structure of the foamy copper, and the copper-cobalt-nickel composite sulfide has good catalytic performance due to the synergistic effect of three metals, so that higher current response can be displayed in the detection process, and amplification of a glucose detection signal is realized.
Drawings
FIG. 1 is a CV diagram of various sulfide electrodes in accordance with aspects of the present invention;
FIG. 2 is a scanning electron microscope image of the copper-cobalt-nickel composite sulfide of the present invention;
FIG. 3 is a surface scanning energy spectrum of the elements of the Cu-Co-Ni composite sulfide electrode of the present invention;
FIG. 4 is a graph of the time current of the present invention with different concentrations of glucose added to a 0.1M sodium hydroxide solution;
FIG. 5 is a graph of the corresponding glucose concentration versus current in FIG. 4;
FIG. 6 is a graph of the time current application of the enzyme-free glucose sensor of the present invention to a sodium hydroxide solution of glucose of small molecule substances (ascorbic acid (AA), Dopamine (DA), Uric Acid (UA));
FIG. 7 is a graph of stability testing of a copper cobalt nickel complex sulfide electrode of the enzyme-free glucose sensor of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples and figures, which are set forth to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
(1) Cutting the foam copper into 0.8 × 1.5 cm2Blocks of (4) were sonicated in acetone and ethanol at 100kHz for 10 min each.
(2) Preparing 0.5M cobalt sulfate and nickel sulfate mixed solution (wherein the molar ratio of cobalt to nickel is 1: 1) A, and then preparing 0.5M sodium sulfide solution. For comparison, a 0.5M cobalt sulfate solution B and a 0.5M nickel sulfate solution C were prepared separately.
(3) And soaking the foamy copper into the solution A for 1 min, vertically placing the foamy copper on filter paper for 15 s by using a pair of tweezers, soaking the foamy copper into the sodium sulfide solution for 1 min, and washing the foamy copper with water to obtain the copper-cobalt-nickel composite sulfide electrode. For comparison, another three pieces of foam copper are taken, one piece of foam copper is directly immersed in the sodium sulfide solution for 1 min, and the copper sulfide electrode is obtained after the other piece of foam copper is washed by water; and respectively soaking the other two sheets in the solutions B and C for 1 min, vertically placing the two sheets on filter paper for 15 s by using forceps, respectively soaking the two sheets in the sodium sulfide solution for 1 min, and washing the two sheets with water to obtain the copper-cobalt composite sulfide electrode and the copper-nickel composite sulfide electrode.
(4) Drying the different sulfide electrodes obtained in the step (3) at 60 ℃ for 3 h.
(5) And (3) taking the different sulfide electrodes obtained in the step (4) as working electrodes, forming a three-electrode system with a counter electrode (platinum wire electrode) and a reference electrode (Ag/AgCl/3M KCl), connecting the three-electrode system with an electrochemical workstation of Shanghai Chenghua CHI660C to form an electrochemical sensor, and testing CV curves of the different sulfide electrodes in 0.5M glucose by taking 0.1M sodium hydroxide solution as electrolyte. As shown in fig. 1, under the same conditions, the current response value of the copper-cobalt-nickel composite sulfide electrode is the largest, which indicates that the copper-cobalt-nickel trimetal composite sulfide generates a synergistic effect and increases the current response value.
Example 2
(1) Cutting the foam copper into 0.8 × 1.5 cm2Blocks of (4) were sonicated in acetone and ethanol at 100kHz for 10 min each.
(2) 0.5M cobalt sulfate and nickel sulfate mixed solution (the molar ratio of cobalt to nickel is 1: 1) is prepared, and 0.5M sodium sulfide solution is prepared.
(3) And (3) soaking the foamy copper into the cobalt-nickel mixed solution for 1 min, vertically placing the foamy copper on filter paper for 15 s by using a pair of tweezers, soaking the foamy copper into the sodium sulfide solution for 1 min, and washing the foamy copper with water to obtain the copper-cobalt-nickel composite sulfide electrode.
(4) And (4) drying the copper-cobalt-nickel composite sulfide electrode obtained in the step (3) at 60 ℃ for 3 h.
(5) And (3) taking the copper-cobalt-nickel composite sulfide electrode obtained in the step (4) as a working electrode, forming a three-electrode system with a counter electrode (platinum wire electrode) and a reference electrode (Ag/AgCl/3M KCl), and connecting the three-electrode system with an electrochemical workstation of Shanghai Chenhua CHI660C to form an electrochemical sensor, thus obtaining the copper-cobalt-nickel composite sulfide enzyme-free glucose electrochemical sensor.
In fig. 2, (a), (b), and (c) are scanning electron microscope images of the copper-cobalt-nickel composite sulfide under different times, and it can be seen that in this case, the copper-cobalt-nickel composite sulfide obtained by using the copper foam and the ion layer adsorption and reaction method is a nanoparticle with uniform particles and has a loose and porous structure, so that it has a large specific surface area, and provides a basis for efficient catalytic reaction.
Fig. 3 is a surface scanning energy spectrum of elements(s), (b), cu (c), co (d), and ni (e)) of the cu-co-ni composite sulfide electrode (a), which illustrates that the cu-co-ni composite sulfide electrode prepared in this case contains four elements of cu, co, ni, and s and is uniformly distributed.
Adding glucose with different concentrations into 0.1M sodium hydroxide solution serving as electrolyte under stirring at a constant potential of 0.6V, and performing electrochemical sensing determination on the glucose by a current-time curve test method (I-t). FIG. 4 and FIG. 5 are a current-time graph and a linear relationship graph of glucose concentration and current, respectively, and the detection of glucose by the enzyme-free sensor of the present invention shows two linear sensitivities between 0.005 and 0.37 mM and 8677.6 muA. mM-1·cm-2And the detection limit is 2.7 mu M. The sensitivity is 2610 muA. mM between 0.37 and 1.37 mM-1·cm-2. In the embodiment 1 of the invention, the constructed copper-cobalt-nickel trimetal sulfide enzyme-free glucose sensor has higher sensitivity, wider linear range and lower detection limit, and has better application potential in the field of real-time blood glucose detection.
Example 3
The constructed copper-cobalt-nickel trimetal sulfide enzyme-free glucose sensor is applied to an anti-interference performance test, and the specific steps and results are as follows: to a 0.1M NaOH solution was added 0.1 mM glucose, 0.01 mM Ascorbic Acid (AA), 0.01 mM Dopamine (DA), 0.01 mM Uric Acid (UA), 0.1 mM glucose, respectively, and the time-current curve was tested. As shown in fig. 6, the copper-cobalt-nickel enzyme-free glucose sensor constructed by the invention has no obvious current response phenomenon observed on common small molecular substances such as ascorbic acid, uric acid and dopamine in human blood, has good anti-interference capability, and the presence of common interferents in blood does not influence the determination result of the modified electrode on the glucose concentration.
Example 4
The stability of the constructed copper-cobalt-nickel trimetal sulfide enzyme-free glucose sensor is tested, and the specific steps and results are as follows: the current response value on the first day was obtained by adding 0.5 mM glucose solution to 0.1M NaOH solution at a test potential of 0.6V with constant stirring. The electrode was then stored in a refrigerator at 4 ℃ and the peak current response intensity of the electrode to a 0.5 mM glucose solution was measured every seven days under the same conditions for 28 days for 5 consecutive determinations. The current intensity was measured as I on the first day0The ratio of the current response intensity of each subsequent day to the current response intensity of the first day (I/I)0) The relationship with time is shown in fig. 7. After 28 days, the current response intensity ratio of the copper-cobalt-nickel trimetal sulfide enzyme-free glucose sensor is still kept above 93%, which indicates that the sensor has good stability and can realize long-time continuous measurement.
Claims (8)
1. The preparation method of the enzyme-free glucose electrochemical sensor is characterized by comprising the following steps of:
(1) pretreating a substrate;
(2) preparing a mixed metal ion solution and a sulfide solution;
(3) preparing a copper-cobalt-nickel sulfide modification layer on a substrate in an in-situ growth manner;
(4) drying the prepared copper-cobalt-nickel sulfide electrode;
(5) and (4) taking the copper-cobalt-nickel composite sulfide electrode prepared in the step (4) as a working electrode, forming a three-electrode system with a counter electrode and a reference electrode, and connecting the three-electrode system with an electrochemical workstation to form an electrochemical sensor, thus obtaining the copper-cobalt-nickel composite sulfide enzyme-free glucose electrochemical sensor.
2. The production method according to claim 1, wherein in the step (1), the substrate is copper foam; the pretreatment is to cut the foam copper into 0.8 multiplied by 1.5 cm2And sonicated in acetone and ethanol at 100kHz for 10 min each.
3. The method according to claim 1, wherein in the step (2), the mixed metal ion solution is a cobalt-nickel ion mixed solution having a composition of a mixed aqueous solution of cobalt sulfate and nickel sulfate, and the sulfide solution is an aqueous solution of sodium sulfide.
4. The preparation method according to claim 3, wherein in the step (2), the molar ratio of cobalt to nickel in the cobalt-nickel ion mixed solution is 1: 1, the total concentration of the mixed solution is 0.5M, and the concentration of the sodium sulfide solution is 0.5M.
5. The preparation method according to claim 1, wherein in the step (3), the copper-cobalt-nickel complex sulfide modification layer is prepared by in-situ growth on the substrate by using an ionic layer adsorption and reaction method: and immersing the electrode substrate into the cobalt-nickel mixed solution for 1 min, vertically placing the electrode substrate on filter paper for 15 s by using a pair of tweezers, immersing the electrode substrate into a sodium sulfide solution for 1 min, and washing the electrode substrate by using water to obtain the copper-cobalt-nickel composite sulfide electrode.
6. The method according to claim 1, wherein in the step (4), the drying temperature of the copper-cobalt-nickel composite sulfide electrode is 60 ℃ and the drying time is 3 hours.
7. The method of claim 1, wherein in the step (5), the counter electrode is a platinum wire electrode and the reference electrode is Ag/AgCl/3M KCl.
8. An electrochemical sensor for non-enzymatic glucose comprising the method of making the non-enzymatic glucose electrochemical sensor of any one of claims 1-7.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114354692A (en) * | 2022-01-04 | 2022-04-15 | 合肥工业大学 | Preparation method and application of enzyme-free glucose sensor electrode material |
CN114652306A (en) * | 2022-03-17 | 2022-06-24 | 电子科技大学 | MOFs-based fingertip contact type noninvasive sweat glucose sensor and method |
CN114910526A (en) * | 2022-05-24 | 2022-08-16 | 四川大学 | High-sensitivity glucose sensor and preparation method and application thereof |
CN115656288A (en) * | 2022-10-20 | 2023-01-31 | 嘉庚创新实验室 | Foamy copper with surface coated with nano copper and application of foamy copper as enzyme-free glucose detection sensor |
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